The polyfluoroalkyl-substituted compounds obtained by the process of this invention can be represented by the following formulae: ##STR1## wherein: X represents a chlorine atom, a bromine atom or an iodine atom;
R.sup.1 and R.sup.2 each represents hydrogen, a halogen atom (F, Cl, Br or I) or a poly- or perfluoroalkyl group having 1 to 20 carbon atoms; PA0 R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 each represents hydrogen; a halogen atom (F, Cl, Br or I); a poly- or perfluorocarbon group having 1 to 20 carbon atoms; or a substituted or unsubstituted alkyl, vinyl, aryl, alkyloxy, acyloxy, amino, amide, silyl, silyloxy, alkylthio, alkoxycarbonyl, acyl, formyl or cyano group wherein the alkyl group has 1 to 10 carbon atoms and wherein the substituent is selected from the group consisting of an alkyl group having 1 to 5 carbon atoms, a halogen atom, an alkoxy group having 1 to 5 carbon atoms, a trialkylsilyl or trialkylsilyloxy group having 1 to 5 carbon atoms in each alkyl moiety, a hydroxy group, an alkoxycarbonyl group having 1 to 5 carbon atoms in the alkoxy moiety and an aryl group; PA0 R.sup.9 and R.sup.10 each represents hydrogen, a halogen atom (F, Cl, Br or I) or a poly- or perfluoroalkyl group having 1 to 20 carbon atoms; PA0 R.sup.11 and R.sup.12 each represents hydrogen, an alkyl group having 1 to 10 carbon atoms or an aryl group; PA0 X.sup.1 represents a halogen atom (F, Cl, Br or I); and wherein at least one of R.sup.9, R.sup.10 and X.sup.1 represents a fluorine atom or a poly- or perfluoroalkyl group having 1 to 20 carbon atoms. PA0 R.sup.1 and R.sup.2 each represents hydrogen, a halogen atom or a poly- or perfluoroalkyl group having 1 to 20 carbon atoms; PA0 R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 each represents hydrogen; a halogen atom; a poly- or perfluorocarbon group having 1 to 20 carbon atoms; or a substituted or unsubstituted alkyl, vinyl, aryl, alkyloxy, acyloxy, amino, amide, silyl, silyloxy, alkylthio, alkoxycarbonyl, acyl, formyl or cyano group wherein the alkyl group has 1 to 10 carbon atoms and wherein the substituent is selected from the group consisting of an alkyl group having 1 to 5 carbon atoms, a halogen atom, an alkoxy group having 1 to 5 carbon atoms, a trialkylsilyl or trialkylsilyloxy group having 1 to 5 carbon atoms in each alkyl moiety, a hydroxy group, an alkoxycarbonyl group having 1 to 5 carbon atoms in the alkoxy moiety and an aryl group; PA0 R.sup.9 and R.sup.10 each represents hydrogen, a halogen atom or a poly- or perfluoroalkyl group having 1 to 20 carbon atoms; PA0 R.sup.11, R.sup.12, R.sup.13, R.sup.14 and R.sup.15 each represents hydrogen, an alkyl group having 1 to 10 carbon atoms or an aryl group; PA0 X.sup.1 represents a halogen atom; and
The polyfluoroalkyl-substituted compounds of the formulae (III) and (V) are useful as intermediates for surface active agents, water-repellents, oil-repellents, fiber treating agents, etc. as disclosed in, for example, Japanese Patent Publication (Examined) Nos. 37644/75 and 8683/78, U.S. Pat. No. 3,979,469 and British Patent No. 1,411,200, and the polyfluoroalkyl-substituted compounds of the formula (VIII), i.e., 3-polyfluoroalkyl-1-propenes, are useful as intermediates for fiber treating agents as disclosed in U.S. Pat. No. 3,843,735 and British Patent No. 1,377,235.
Hitherto, polyfluoroalkyl-substituted compounds of the formulae (III) and (V) have been prepared by (1) a method comprising radiating a mixture of an iodoperfluoroalkane and an olefin or an acetylene compound with light as disclosed in, for example, R. N. Haszeldine, J. Chem. Soc., 2856 (1949); and ibid, 3037 (1950), (2) a method comprising reacting an iodoperfluoroalkane with an olefin or an acetylene compound at a temperature higher than 200.degree. C. as disclosed in, for example, R. N. Haszeldine, J. Chem. Soc., 2789 (1950); and R. N. Haszeldine and B. R. Steele, J. Chem. Soc., 1199 (1953), (3) a method comprising heat-reacting an iodoperfluoroalkane with an olefin or an acetylene compound in the presence of a radical reaction initiator as disclosed in, for example, K. Baum, C. D. Bedford and R. J. Hunadi, J. Org. Chem., 47, 2251, or (4) a method comprising reacting a haloperfluoroalkane with an olefin in the presence of an amine and a metal salt of the Group of Ia to IVa, Ib to VIIb or VIII of the Periodic Table or in the presence of an amine-metal salt complex as disclosed in Japanese Patent Publication (Unexamined) No. 5368/72, Japanese Patent Publication (Examined) Nos. 37644/75 and 8683/78.
However, the above conventional method (1) requires radiation with light for a prolonged period of time and has a disadvantage in that the yield of the desired product is not satisfactory. Also, the above conventional method (2) requires a reaction at a high temperature for a long period of time in order to obtain the desired product in a satisfactory yield and, further, it requires a reactor which is resistant to high temperature and high pressure. The above conventional method (3) requires a reaction at a high reaction temperature for a long period of time and also requires a radical reaction initiator which is unstable and dangerous and, therefore, which must be handled with great care. In addition, the radical reaction initiator used in the method (3) is not recovered for reuse. The above conventional method (4) requires a reaction at a high temperature for a long period of time and, further, the yield of the desired product is generally poor, as evidenced by Comparative Examples hereinafter described.
On the other hand, the 3-polyfluoroalkyl-1-propenes of the formula (VIII) have been conventionally prepared by a method comprising adding a perfluoroalkyl iodide to an allyl alkyl ether or an allyl ester to prepare the corresponding 3-perfluoroalkyl-2-iodo-1-propyl alkyl ether or 3-perfluoroalkyl-2-iodo-1-propyl ester, respectively, followed by treating the resulting ether or ester with zinc as disclosed in Japanese Patent Publication (Unexamined) No. 34805/73. However, this conventional method requires the reactions in two steps and also gives the product in poor yield. Further, the starting material used in this conventional method is limited to compounds having a perfluoroalkyl group, and, therefore, starting compounds having a halopolyfluoroalkyl group cannot be used in this method.